流延法制备聚酰亚胺薄膜工艺研究

以均苯四甲酸二酐、4，4＇-二胺基二苯醚为原料，通过缩聚反应制备了聚酰胺酸，采用凝胶渗透色谱（GPC）考察了反应时间对产物重均摩尔质量的影响；测定了干燥过程中聚酰胺酸凝胶膜溶剂含量的变化；并利用电子万能试验机研究了聚酰胺酸薄膜的拉伸工艺。结果表明：聚酰胺酸的适宜反应时间为6h，此时其重均摩尔质量趋于稳定。随着干燥温度的升高和时间的延长，凝胶膜的溶剂含量逐渐减少。分析得到较好的拉伸条件是干燥温度为130℃，溶剂质量分数为30％左右的凝胶膜。聚酰亚胺薄膜经拉伸后，其拉伸强度和模量均随拉伸比的增大而增加。     

高温热处理对聚酰亚胺薄膜性能的影响

研究了高温热处理对聚酰亚胺(PI)薄膜拉伸性能和热性能的影响。在薄膜完全环化后,随着热处理温度的升高,薄膜的拉伸强度、弹性模量先增大后基本保持不变,断裂伸长率先保持不变后明显降低,热膨胀系数也显著降低,而薄膜的玻璃化转变温度略有增大。高温热处理工艺可制备高强度和低热膨胀系数的高性能PI薄膜。     

热塑性聚酰亚胺复合材料导热性能研究

采用稳态热板法测定铜粉（Cu）填充热塑性聚酰亚胺（TPI）复合材料的热导率，研究了Cu填充量对复合材料的力学性能和导热性能的影响，初步探讨了温度与复合材料热导率的关系。通过扫描电子显微镜观察了复合材料的微观形态。在此基础上，理论计算复合材料热导率。研究表明，Cu填充TPI可有效提高复合材料力学性能和导热性能。当Cu体积分数提高到26％时，填料聚集形成导热链，Cu／TPI复合材料的热导率是纯TPI树脂的3．5倍；当填料含量低于10％时，Maxwell—Eucken模型适合预测复合材料热导率；基于导热链考虑的Y．Agan模型可较好地反映复合材料热导率随填料含量的变化情况；随着温度的升高，Cu／TPI复合材料热导率先增大后趋于平缓。     

高导电纳米银/聚酰亚胺复合薄膜的制备及其性能研究

通过对聚酰亚胺(PI)薄膜进行碱溶液水解、离子交换和热处理制备出具有表面导电性的聚酰亚胺银复合薄膜,并研究了影响聚酰亚胺银复合薄膜导电性的因素。结果表明,一定的薄膜厚度、碱溶液处理时间、合适的固化时间和固化温度都有利于制备出高导电性的复合薄膜。该复合薄膜保持了聚酰亚胺薄膜的基本力学性能,并且银原子与聚合物之间有良好的黏附性能。该制备方法简单,成本低,易于大规模生产。     

聚合物溶液流变曲线及粘温特性研究

用长庆油田北三区处理后清水、聚丙烯酰胺配制了聚合物母液和目的液,聚合物母液浓度5000mg/L、目的液浓度2000mg/L,测量温度为10~60℃,剪切速率为1~100s~(-1),考察了剪切速率、温度对不同浓度聚合物的流变性、粘度影响。结果表明,聚合物溶液的粘度随剪切速率的增大不断降低,同一剪切速率下聚合物溶液的表观粘度随温度的升高也有所下降,随着测量温度的升高,聚合物溶液的屈服应力逐渐降低,稠度系数K逐渐增大而流变行为指数逐渐减小,在实际测量温度范围内,聚合物溶液属于非牛顿流体,体现出典型的屈服-假塑性流体特性,剪切速率对聚合物溶液的粘度值影响很大,测量温度对粘度值的影响较小。     

氧化铝掺杂聚酰亚胺纳米复合薄膜的制备与性能研究

通过溶液法，成功地制备了氧化铝掺杂聚酰亚胺纳米复合薄膜。探讨了Al2O3用量对聚酰亚胺纳米复合薄膜拉伸强度、热性能、电气强度的影响。结果发现，当Al2O3的质量分数达到5％时，整个复合体系的拉伸强度达到最大，相对于聚酰亚胺母体，复合材料的拉伸强度提高了16％；当Al2O3用量较小时，对聚酰亚胺纳米复合薄膜的Td10的影响不大，但当Al2O3的质量分数超过15％时，Td10则随Al2O3用量的增加而下降；同时实验结果表明，Al2O3的引入可以在一定程度上改善其复合体系的电气强度。     

聚酰亚胺薄膜拉伸工艺的研究

阐述了热固性聚酰亚胺薄膜的拉伸可行性,初步确定了聚酰胺酸薄膜的初始溶剂含量、拉伸温度、以及拉伸速度等因素对薄膜性能的影响。     

聚酰亚胺-聚四氟乙烯复合材料的制备和表征

利用共混挤出工艺制备聚酰亚胺-聚四氟乙烯(PI-PTFE)复合材料,考察PTFE含量对复合材料热性能、摩擦性能及力学性能的影响。结果表明:制得的PI-PTFE复合材料两相不相容,复合材料的最高使用温度为250℃,在250℃以下复合材料的尺寸稳定性较好,其线膨胀系数随PTFE含量的增加而增大,不受热循环历程的影响;复合材料分解质量损失5%的温度(t5d)为525℃,热分解速率随PTFE含量的增加而增大;干摩擦时,随PTFE含量的增加,复合材料的摩擦因数降低,磨损率呈上升趋势;复合材料的拉伸强度、弯曲强度和硬度均随PTFE含量的增加而降低,就力学性能而言,PTFE的添加量不超过20%为宜。     

聚酰胺酸纺丝溶液的流变性能研究

由均苯四酸二酐(PMDA)和4,4'-二氨基二苯醚(ODA)在N,N-二甲基乙酰胺(DMAc)中共聚合制得聚酰亚胺前驱体——聚酰胺酸的纺丝溶液,采用哈克流变仪研究了溶液的流变性能。结果表明:聚酰胺酸溶液属于切力变稀的非牛顿流体;溶液的表观黏度随溶液温度的升高而降低,随溶液浓度的升高或聚合物特性黏度的增大而增大。溶液温度的升高、浓度的降低或聚合物特性黏度的减小均使得聚酰胺酸溶液呈现切力变稀行为的临界剪切速率变大,使得溶液的非牛顿指数增大,同时使得溶液的结构黏度指数减小。溶液的黏流活化能随剪切速率的增加或随溶液浓度的增高而下降。     

GE推出极端环境用新的Extem树脂

GE塑料公司推出Extem热塑性聚酰亚胺（TPI）树脂，这是一种无定形聚合物新家族，具有卓越的性能，可免除某些半结晶材料、酰亚胺类热固性塑料和其他无定形热塑性塑料的缺点。     

新型热塑性聚酰亚胺改性环氧胶粘剂的研制

采用含羧基聚酰亚胺粉末,对环氧树脂胶粘剂进行改性,制得新型环氧胶粘剂,其拉伸剪切强度可达30.0MPa以上,初始分解温度大于368.5℃。随着聚酰亚胺量的增加,其耐热性也相应提高。此外,环氧胶粘剂体系的疏水性也有一定程度的提高。     

High-performance polymer films. III. Preparation and characterization

A series of polyimide and copolyimide films were prepared by film casting, drying, and thermal imidization from the respective precursor poly(amic acid) (PAA) and copoly(amic acid) solutions derived from two dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and two diamines, 4,4′-oxydianiline (ODA) and a proprietary aromatic diamine (PD) as monomers. Depending on the solution's inherent viscosity value (molecular weight) and the nature of the polymer chains (derived from rigid or flexible monomers), precursor poly(amic acid) and copoly(amic acid) solution concentrations of 8–12% (w/w) were found to be suitable for the preparation of good quality polyimide/copolyimide films. The recovery of film toughness and creasability from the brittleness at the intermediate temperature of the cure cycle depended not only on the molecular weight of the precursor poly(amic acids)/copoly(amic acids) but also on their chain flexibility. The poly(amic acid) derived from both rigid dianhydride and diamine practically gave rise to a brittle film of polyimide even after curing to 360°C. The resulting polyimide and copolyimide films were compared with Du Pont's Kapton H film. The density of the films was in the range 1.39–1.42 g/cm³. The thickness of most of the films was in the range 20–30 μm. The HPF 3 film, based on PMDA–PD, appeared to be highly colored (reddish brown), and the HPF 2 film, based on BTDA–ODA, had the lightest yellow coloring among the films in this investigation, including Kapton H film. HPF 2, HPF 6, and HPF 8 films were more amorphous than the other films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 976–988, 2001     

Effect of film formation process on residual stress of poly(p-phenylene biphenyltetracarboximide) in thin films

Soluble poly(p-phenylene biphenyltetracarboxamine acid) (BPDA-PDA PAA) precursor, which was synthesized from biphenyltetracarboxylic dianhydride and p-phenylene diamine in N-methyl-2-pyrrolidone (NMP), was spin-cast on silicon substrates, followed by softbake at various conditions over 80–185°C. Softbaked films were converted in nitrogen atmosphere to be the polyimide films of ca. 10 μm thickness through various imidizations over 120–400°C. Residual stress, which is generated at the polymer/substrate interface by volume shrinkage, polymer chain ordering, thermal history, and differences between properties of the polymer film and the substrate, was measured in situ during softbake and subsequent imidization processes. Polymer films imidized were further characterized in the aspect of polymer chain orientation by prism coupling and X-ray diffraction. Residual stress in the polyimide film was very sensitive to all the film formation process parameters, such as softbake temperature and time, imidization temperature, imidization step, heating rate, and film thickness, but insensitive to the cooling process. Softbaked precursor films revealed 9–42 MPa at room temperature, depending on the softbake temperature and time. That is, residual stress in the precursor film was affected by the amount of residual solvent and by partial imidization possibly occurring during softbake above the onset of imidization temperature, ca. 130°C. A lower amount of residual solvent caused higher stress in the precursor film, whereas a higher degree of imidization led to lower stress. Partially imidized precursor films were converted to polyimide films revealing relatively high stresses. After imidization, polyimide films exhibited a wide range of residual stress, 4–43 MPa at room temperature, depending on the histories of softbake and imidization. Relatively high stresses were observed in the polyimide films which were prepared from softbaked films partially imidized and by rapid imidization process with a high heating rate. The residual stress in films is an in-plane characteristic so that it is sensitive to the degree of in-plane chain orientation in addition to the thermal history term. Low stress films exhibited higher degree of in-plane chain orientation. Thus, residual stress in the film would be controlled by the alignment of polyimide chains via the film formation process with varying process parameters. Conclusively, in order to minimize residual stress and to maximize in-plane chain orientation, precursor films should be softbaked for 30 min-2 h below the onset imidization temperature, ca. 130°C, and subsequently imidized over the range of 300–400°C for 1–4 h by a two-step or multi-step process with a heating rate of ? 5.0 K min⁻¹, including a step to cover the boiling point, 202°C, of NMP. In addition, the final thickness of the imidized films should be <20 μm. © 1997 Elsevier Science Ltd.     

Carbon nanotube reinforced rigid‐rod polyimide

Multiwalled carbon nanotube/rigid‐rod polyimide composite films have been prepared by casting a solution of precursor polymer (polyamide acid) containing multiwalled carbon nanotubes (MWNTs) into thin films, followed by a thermal imidization treatment. The composite films were characterized by FTIR, TEM, DSC, TGA and TMA, and the film tensile properties were also examined. The presence of 1.0% MWNTs in the polymer matrix led to more than twofold increase in tensile strength of the rigid‐rod polyimide composite films and improved thermal stability, but reduced in thermal deformation. However, the tensile property did not show further increase when the film contained higher composition of MWNTs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multilayer polyimide nanocomposite films synthesis process optimization impact on nanoparticles dispersion and their dielectric performance

The preparation of polyimide (PI)/nanocomposite films and their thickness are a complex process with some ambiguous variables that are involved in the synthesis process. Therefore, it is crucial to understand those variables and reveal the chemistry behind them. Several methods have been probed until an optimal synthesis process was found. A detailed synthesis process optimization is described in this article to understand all variables, which can influence the molecular weight of polyamic acide (PAA) solution, the thickness of films, and nanoparticles dispersion. The spin coating technique was used to control the thickness of single and multilayer PI/nanocomposite films, which reveals that the thickness of the casted PI film depends on several factors, such as the viscosity, molecular weight of the PAA solution, and the spin speed of spin coater. Factors, which can influence the molecular weight of PAA solution, are discussed in detail. After completing the synthesis process, the single and multilayer PI nanocomposite films are characterized experimentally. The results reveal that using a thin layer of nanocomposite on PI film in the form of a multilayer structure improves the nanoparticles dispersion and thereafter its dielectric properties.     

Effect of mechanical treatments on orientation behavior and spectral properties of azoderivative dyes incorporated in poly(vinyl alcohol) films

Various azoderivative dyes were incorporated in uncolored poly(vinyl alcohol) (PVOH). One type of film was obtained by drying the layer of solution cast on glass plate. The other type was obtained by rubbing the PVOH layer before complete drying. Linear birefringence and dichroism of dyed polymer films were investigated as a function of stretching degree. An increase in the linear birefringence was found with increasing stretching degree for both uncolored and colored films. Dichroism of the PVOH films depends on the dye chemical structure and also on the stretching degree of both non-rubbed and rubbed and dyed PVOH samples. Molecular modeling was used to examine interactions occurring between PVOH and the embedded dye molecule. These stretching degree dependencies were approximated mathematically, which was used to describe the behavior of some components of interference filters.     

Synthesis and properties of 6FDA‐BisAAF‐PPD copolyimides for microelectronic applications

In this work, fluorine‐containing copolyimides were synthesized from 6FDA dianhydride and different ratios of BisAAF and PPD diamines. Properties, such as composition, viscosity, dielectric constant, glass‐transition temperature, thermal decomposition temperature, tensile characteristics, and transmittance, were investigated by using elemental analysis, viscometry, Fourier transform infrared spectrometry, differential scanning calorimetry, a thermogravimetric analyzer, a tensile tester, and UV–visible spectrophotometry. After curing at 300°C for 1 h, imidization was observed, as indicated the appearance of an absorption peak of the carbonyl of the imide at 1780 cm^?1 (C?O asymmetry stretching). The inherent viscosity increased with an increasing PPD mole fraction, from 0.40 dL/g of pure 6FDA‐BisAAF to 0.84 dL/g of pure 6FDA‐PPD. The dielectric constant decreased with increasing fluorine content. The glass‐transition temperature increased with an increasing PPD mole fraction; the values increased from 317°C with pure 6FDA‐BisAAF polyimide to 364°C with pure 6FDA‐PPD polyimide. The 5% weight loss temperature (T_d) of the copolyimides was around 530°C in air and 540°C in a nitrogen atmosphere. The tensile modulus and tensile strength gradually increased with an increasing PPD molar fraction. The transmittance of 6FDA‐BisAAF‐PPD copolyimides was greater than 90% at wavelengths above 500 nm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2064–2069, 2005     

Synthesis and characterization of melt-processable polyimides derived from diaminodiphenylsulfone and benzophenone tetracarboxylic dianhydride with excellent heat resistance and thermoplasticity

Polyimide has excellent heat resistance, dielectric properties, and mechanical properties, and has a wide range of applications in aerospace, electronic packaging, and insulating materials. However, traditional polyimide is difficult to melt and dissolve, and its processing is difficult, which has become an important reason limiting its practical application. Therefore, the development of high temperature-resistant thermoplastic polyimide has become a research hotspot. To prepare high temperature-resistant thermoplastic polyimide materials, a series of thermoplastic polyimides was successfully prepared using 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 3,3′-diaminodiphenylsulfone, 2,3′,3,4′-benzophenone tetracarboxylic dianhydride, 9,9-bis(4-aminophenyl)fluorene, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane via a two-step method. The effects of non-coplanar structure and bulky groups on the solubility, processability, and thermal properties of polyimide were studied. The structure, heat resistance and thermoplasticity of polyimide were characterized via various methods. The results show that the glass transition temperature of the prepared thermoplastic polyimide is between 292 and 302°C, and has excellent thermal resistance. The processing viscosity of polyimides is as low as 9210 Pa.s, and it has a certain degree of processing properties. It may be designed to be used in high temperature-resistant hot melt adhesives for structural components, high temperature-resistant melt processing resins, or thermoplastic composite materials used in the field of aerospace in the future.     

聚酰亚胺的合成及其膜的制备

先在四氢呋喃/甲醇(质量比为4:1)混合溶剂体系中合成聚酰胺酸(PAA),后在真空烘箱中(200℃/h)形成聚酰亚胺(PI)膜,并通过IR和TG/DTG对产物进行了表征,结果表明能得到耐高温的Pl膜。     

Residual stress and mechanical properties of polyimide thin films

Four different structure polyimide thin films based on 1,4‐phenylene diamine (PDA) and 4,4′‐oxydianiline (ODA) were synthesized by using two different dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), and their residual stress behavior and mechanical properties were investigated by using a thin film stress analyzer and nanoindentation method. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. The morphological structure of polyimide thin films was characterized by X‐ray diffraction patterns and refractive indices. The residual stress was in the range of ?5 to 38 MPa and increased in the following order: PMDA‐PDA < BPDA‐PDA < PMDA‐ODA < BPDA‐ODA. The hardness of the polyimide films increased in the following order: PMDA‐ODA < BPDA‐ODA < PMDA‐PDA < BPDA‐PDA. The PDA‐based polyimide films showed relatively lower residual stress and higher hardness than the corresponding ODA‐based polyimide films. The in‐plane orientation and molecularly ordered phase were enhanced with the increasing order as follows: PMDA‐ODA < BPDA‐ODA < BPDA‐PDA ～ PMDA‐PDA. The PDA‐based polyimides, having a rigid structure, showed relatively better‐developed morphological structure than the corresponding ODA‐based polyimides. The residual stress behavior and mechanical properties were correlated to the morphological structure in polyimide films. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009